US8143439B2 - Zeolite-catalyzed preparation of alpha-hydroxy carboxylic acids and esters thereof - Google Patents

Zeolite-catalyzed preparation of alpha-hydroxy carboxylic acids and esters thereof Download PDF

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US8143439B2
US8143439B2 US12/614,251 US61425109A US8143439B2 US 8143439 B2 US8143439 B2 US 8143439B2 US 61425109 A US61425109 A US 61425109A US 8143439 B2 US8143439 B2 US 8143439B2
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US20100121096A1 (en
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Esben Taarning
Saravanamurugan Shunmugavel
Martin Spangsberg Holm
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Topsoe AS
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Haldor Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides

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  • the present invention relates to the preparation of ⁇ -hydroxy carboxylic acid compounds by catalytic conversion of carbohydrates and carbohydrate like material.
  • the invention is a process for the preparation of lactic acid compounds as main product and 2-hydroxy-3-butenoic acid as valuable by-product from glucose, fructose, sucrose, xylose or glycolaldehyde in presence of a solid Lewis acidic zeolite.
  • Lactic acid is an important chemical that is used for production of biodegradable polymers and solvents.
  • the industrial production of lactic acid is based on the anaerobic fermentation of glucose and sucrose using microbial fermentation.
  • the major complications associated with this process are the need to neutralize lactic acid with a stoichiometric amount of base during the fermentation process and the energy intensive work-up of lactic acid from the aqueous fermentation broth.
  • Lewis acidic zeolites such as Sn-Beta show surprisingly high activity and selectivity for the conversion of carbohydrates or carbohydrate like compounds such as sucrose, glucose, fructose, xylose and glycolaldehyde to esters of lactic acid and 2-hydroxy-3-butenoic acid according the following reaction scheme:
  • Part A hydrolysis of sucrose and fragmentation to form triose sugars (dihydroxyacetone and glyceraldehyde).
  • Part B dehydration of the triose sugars to form methyl glyoxal.
  • Part C addition of methanol to methyl glyoxal to form a hemiacetal followed by redox isomerisation of the hemiacetal to produce methyl lactate.
  • Pursuant to the above finding this invention is a process for the production of lactic acid and 2-hydroxy-3-butenoic acid or esters thereof by conversion of glucose, fructose, sucrose, xylose or glycolaldehyde dissolved in a solvent in presence of a solid Lewis acidic catalyst.
  • a useful solid Lewis acidic catalyst is a zeotype material, preferably containing a tetravalent metal being incorporated in its framework, such as Sn, Pb, Ge, Ti, Zr and/or Hf. Most preferably, the zeotype material contains tetravalent Sn and/or Ti.
  • the zeotype material has preferably a structure type BEA, MFI, MEL, MTW, MOR, LTL or FAU, such as zeolite beta and ZSM-5.
  • a further preferred zeotype materiel is TS-1.
  • Further useful catalysts are Lewis acidic mesoporous amorphous materials, preferably with the structure type MCM-41 or SBA-15.
  • Lactic acid and 2-hydroxy-3-butenoic acid are prepared in an aqueous solution of the sugars containing the catalyst.
  • the solvent is an alcohol, such as methanol and ethanol, optionally admixed with a secondary solvent.
  • the secondary solvent may be water, dimethyl sulfoxide or a hydrocarbon solvent.
  • Higher esters of lactic acid and 2-hydroxy-3-butenoic acid may be prepared by use of higher alcohols as solvent.
  • ethyl lactate and ethyl 2-hydroxy-3-butenoate are prepared by using ethanol and/or a mixture of ethanol and a secondary solvent, such water in the case of 96% ethanol.
  • i-propyl esters are prepared when 2-propanol is used as the solvent and the n-butyl esters are prepared by use of 1-butanol as the solvent.
  • the above reactions according to the invention may be conducted in a batch or flow reactor at temperatures in the range of 50-300° C., preferably 100-220° C. and most preferred between 140 and 200° C.
  • Examples 1-5 illustrate a process for the conversion of sucrose, glucose, fructose, xylose and glycolaldehyde in methanol to form methyl lactate and methyl 2-hydroxy-3-butenoate using Sn-BEA as the catalyst.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2250 g of sucrose (0.6576 mmol), 121.3 mg naphthalene (internal standard) and finally with 160.2 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 1.74 mmol of methyl lactate is formed (66%) together with 0.022 mmol methyl 2-hydroxy-3-butenoate (1%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2251 g of glucose (1.250 mmol), 119.3 mg naphthalene (internal standard) and finally with 160.3 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 1.02 mmol of methyl lactate is formed (41%) together with 0.051 mmol methyl 2-hydroxy-3-butenoate (3%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2251 g of fructose (1.250 mmol), 120.0 mg naphthalene (internal standard) and finally with 162.0 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 1.07 mmol methyl lactate is formed (43%) together with 0.068 mmol methyl 2-hydroxy-3-butenoate (4%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2251 g of xylose (1.500 mmol), 121.8 mg naphthalene (internal standard) and finally with 160.0 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.75 mmol of methyl lactate is formed (30%) together with 0.049 mmol methyl 2-hydroxy-3-butenoate (3%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2254 g of glycolaldehyde (3.755 mmol), 119.5 mg naphthalene (internal standard) and finally with 160.0 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.40 mmol of methyl lactate is formed (16%) together with 0.47 mmol methyl 2-hydroxy-3-butenoate (25%).
  • Examples 6-9 illustrate the use of different Lewis acidic catalysts in a process for the conversion of sucrose in methanol to form methyl lactate and methyl 2-hydroxy-3-butenoate.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2251 g of sucrose (0.6575 mmol), 121.0 mg naphthalene (internal standard) and finally with 160.0 mg Sn-MFI (prepared according to method A in Mal et al, Micro. Mater., 12, 1997, 331-340).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.973 mmol of methyl lactate is formed (37%) together with 0.006 mmol methyl 2-hydroxy-3-butenoate (0.3
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2247 g of sucrose (0.6564 mmol), 111.5 mg naphthalene (internal standard) and finally with 165.1 mg Sn-SBA-15 (prepared according to Micro. Meso. Mater., 112, 2008, 97 using SnCl 4 *5H 2 O as the tin source).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.55 mmol of methyl lactate is formed (21%) together with 0.002 mmol methyl 2-hydroxy-3-butenoate (0.1%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2261 g of sucrose (0.6605 mmol), 118.3 mg naphthalene (internal standard) and finally with 160.2 mg Zr-BEA (prepared according to Chem Commun, 2003, 2734).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.977 mmol of methyl lactate is formed (37%) together with 0.036 mmol methyl 2-hydroxy-3-butenoate (2%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2255 g of sucrose (0.6587 mmol), 120.0 mg naphthalene (internal standard) and finally with 163.0 mg Ti-BEA (prepared according to Blasco et al., Chem Commun, 1996, 2367-2368).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.922 mmol of methyl lactate is formed (35%) together with 0.028 mmol methyl 2-hydroxy-3-butenoate (1.4%).
  • Examples 10-14 illustrate a process for the conversion of sucrose in different solvents using Sn-BEA as the catalyst.
  • An autoclave (50 cc microclave) is charged with 8.0 g of water, 0.2256 g of sucrose (0.6590 mmol), and 160.7 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions. HPLC-analysis of the reaction mixture shows that 0.791 mmol of lactic acid is formed (30%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of ethanol, 0.2252 g of sucrose (0.6578 mmol), 118.9 mg naphthalene (internal standard) and finally with 160.0 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 1.03 mmol of ethyl lactate is formed (39%) together with 0.316 mmol ethyl 2-hydroxy-3-butenoate (16%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of 2-propanol, 0.2249 g of sucrose (0.6569 mmol), 119.7 mg naphthalene (internal standard) and finally with 159.7 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.68 mmol of isopropyl lactate is formed (26%) together with 0.237 mmol isopropyl 2-hydroxy-3-butenoate (12%).
  • An autoclave (50 cc microclave) is charged with 8.0 g of 1-butanol, 0.2249 g of sucrose (0.6569 mmol), 121.0 mg naphthalene (internal standard) and finally with 160.5 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.68 mmol of n-butyl lactate is formed (26%) together with 0.164 mmol n-butyl 2-hydroxy-3-butenoate (8%).
  • An autoclave (50 cc microclave) is charged with 8.05 g of methanol and 0.1988 g of water, 0.2252 g of sucrose (0.6578 mmol), 122.6 mg naphthalene (internal standard) and finally with 160.7 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 1.47 mmol of methyl lactate is formed (56%) together with 0.065 mmol methyl 2-hydroxy-3-butenoate (3%).
  • Example 15 illustrates the reuse potential of the Sn-BEA catalyst.
  • An autoclave (50 cc microclave) is charged with 16.07 g of methanol, 0.4504 g of sucrose (1.316 mmol), 115.2 mg naphthalene (internal standard) and finally with 320.8 mg Sn-BEA (prepared according to U.S. Pat. No. 6,306,364).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 3.158 mmol of methyl lactate is formed (60%) together with 0.0513 mmol methyl 2-hydroxy-3-butenoate (1.3%).
  • the used catalyst was dried at 100° C. overnight and calcined at 480° C. for 10 hours reached with a heating ramp of 2° C./min.
  • the regeneration procedure was repeated a 3 rd , 4 th and a 5 th time.
  • Examples 16 and 17 illustrate a fixed-bed process for the conversion of fructose in methanol to give a mixture of methyl lactate and methyl 2-hydroxy-3-butenoate using Sn-BEA and TS-1.
  • a plug flow reactor is charged with 1.0 g of Sn-BEA and pressurized with nitrogen.
  • the reactor is heated to 170° C. and a feed consisting of 11.0 g of fructose dissolved in 500 ml of methanol is passed through the reactor at a rate of 1.0 ml/minute.
  • the resulting methanol solution is collected and analyzed. Analysis of the fraction collected between the 2nd and 3rd hour by GC-MS (durene was used as external standard) shows that 31% methyl lactate is formed together with 7% methyl 2-hydroxy-3-butenoate.
  • a plug flow reactor is charged with 3.0 g of TS-1 (1.53 wt % Ti). The reactor is heated to 170° C. and a feed consisting of 5.0 wt % of fructose in methanol is passed through the reactor at a rate of 0.50 ml/minute. The resulting methanol solution is collected and analyzed. Analysis of the fraction collected between the 1st and 2nd hour by GC-MS (durene was used as external standard) shows that 27.3% methyl lactate is formed together with 2.2% methyl 2-hydroxy-3-butenoate.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2264 g of sucrose (0.6613 mmol), 118.7 mg naphthalene (internal standard) and finally with 162.0 mg Si-BEA (prepared according to Zhu et al., J. Catal., 227, 2004, 1-10).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.046 mmol of methyl lactate is formed (7%). No methyl 2-hydroxy-3-butenoate was formed.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2250 g of sucrose (0.6572 mmol), 119.1 mg naphthalene (internal standard) and finally with 159.7 mg Al-BEA (Si:Al 65:1, prepared according to Zhu et al., J. Catal., 227, 2004, 1-10).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that no methyl lactate has formed.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2251 g of sucrose (0.6575 mmol), 119.1 mg naphthalene (internal standard) and finally 160.0 mg of SnO 2 nanopowder (Sigma-Aldrich) is added.
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.105 mmol of methyl lactate is formed (4%). No methyl 2-hydroxy-3-butenoate was formed.
  • An autoclave (50 cc microclave) is charged with 8.0 g of methanol, 0.2259 g of sucrose (0.6599 mmol), 117.7 mg naphthalene (internal standard) and finally with 7.4 mg SnCl 4 *5H 2 O (0.021 mmol, same amount of tin is used as for the examples with Sn-Beta).
  • the autoclave is closed, charged with 20 bar of argon and heated to 160° C. After the temperature reaches 100° C., the mechanical stirrer is started (500 rpm) and the mixture is heated for 20 hours under these conditions.
  • GC-analysis of the reaction mixture shows that 0.607 mmol of methyl lactate is formed (23%). No methyl 2-hydroxy-3-butenoate was formed.

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Publication number Priority date Publication date Assignee Title
CN107001253A (zh) * 2014-11-28 2017-08-01 托普索公司 由糖制备乳酸酯和2‑羟基‑3‑丁烯酸酯或α‑羟基蛋氨酸类似物的酯的方法
US10100007B2 (en) * 2014-11-28 2018-10-16 Haldor Topsoe A/S Process for preparing esters of lactic acid, and 2-hydroxy-3-butenoic acid or α-hydroxy methionine analogues from sugars
CN107001253B (zh) * 2014-11-28 2019-03-12 托普索公司 由糖制备乳酸酯和2-羟基-3-丁烯酸酯或α-羟基蛋氨酸类似物的酯的方法
US10280136B2 (en) * 2014-11-28 2019-05-07 Haldor Topsoe A/S Process for preparing esters of α-hydroxy methionine from sugars
US10343986B2 (en) * 2014-11-28 2019-07-09 Haldor Topsoe A/S Process for preparing esters of lactic acid, and 2-hydroxy-3-butenoic acid from sugars
RU2710014C2 (ru) * 2014-11-28 2019-12-24 Хальдор Топсеэ А/С Способ получения сложных эфиров молочной кислоты из сахаров

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